Polyacetylene composite, process for production thereof, and method for use thereof

ABSTRACT

A process for the production of a polyacetylene composite is disclosed. A solution containing at least one ionic organic compound represented by the formula (I): ##STR1## wherein M denotes at least one member selected from the group consisting of alkali metals, X and Y are the same or different and represent --O or ##STR2## R 1 , R 2 , R 3  and R 4  each are at least one member selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups of 1 to 5 carbon atoms, and substituted or unsubstituted alkoxy groups of 1 to 5 carbon atoms, or R 1  and R 2  or R 3  and R 4  in combination form a cyclic structure, is applied to a polyacetylene polymer. The coated polyacetylene polymer is then dried.

This application is a divisional of copending application Ser. No.896,633, filed on Aug. 15, 1986 now U.S. Pat. No. 4,686,160 which is adivisional of Ser. No. 679,399, filed on Dec. 7, 1984 now U.S. Pat. No.4,634,636.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a polyacetylene composite comprising a coatingof an ionic organic compound, a process for the production of thecomposite, and a method for the use of the composite.

2. Description of the Prior Art

It has been well known that oxygen-containing organic compounds such ascrown ethers possess an ability to interact with cation species such as,for example, Li⁺, Na⁺, and K⁺. The present inventors, from an extensivestudy of the functions possessed by such oxygen-containing organiccompounds, have discovered specific ionic organic compounds and havefound that these compounds possess an ability to interact with cationspecies such as Li⁺, Na⁺, and K⁺.

As basic characteristics, the aforementioned compounds possess:

(A) Ionic electrical conductivity

(B) Specific interaction with alkali metal ions

(C) Protective activity manifested against anion species.

It has been demonstrated that the specific ionic organic compounds bringabout a highly conspicuous effect in stabilizing n-doped conjugate typepolymers such as polyacetylene.

In recent years, U.S. Pat. No. 4,204,216 and U.S. Pat. No. 4,222,903have disclosed that conjugate type polymers such as polyacetylene arecaused by n-doping with cation species or p-doping with anion species tomanifest phenomenal electrical conductivity. No. EP-36118 has proposed asecondary battery which makes use of a conjugate type polymer such aspolyacetylene. This secondary battery is attracting keen interest as anovel type of secondary battery with an unusually high capacity.Particularly, the polyacetylene which is n-doped with a cation speciesis expected as a highly promising candidate for the negative electrodeactive substance of the non-aqueous type secondary battery which isenjoying a vigorous demand in the trade of secondary batteries.Unfortunately, the aforementioned n-doped polyacetylene disclosed by No.EP-36118 is unusually unstable and this instability constitutes aserious obstacle to practical use.

This instability of the n-doped polyacetylene is interpreted to be afundamental quality ascribable to its extremely active carbanion-likestructure. Any effort to impart improved stability to the n-dopedpolyacetylene has been regarded as nearly impossible.

SUMMARY OF THE INVENTION

The inventors have diligently studied this problem from various anglesand have, consequently, discovered ionic organic compounds representedby the general formula (I): ##STR3## (Wherein M denotes at least onemember selected from the group of alkali metals; X and Y are the same ordifferent and represent --O or R₁, R₂, R₃, and R₄ each are at least onemember selected from the group consisting of hydrogen (substituted orunsubstituted alkyl groups of 1 to 5 carbon atoms, and substituted orunsubstituted alkoxy groups of 1 to 5 carbon atoms; or R₁ and R₂ or R₃and R₄ in combination form a cyclic structure) and found that theseionic organic compounds possess an outstanding ability to stabilize ann-doped polyacetylene.

An object of this invention is to provide a polyacetylene compositewhich comprises a polyacetylene polymer and a coating formed on thepolyacetylene polymer with a specific ionic organic compound and whichovercomes the disadvantage of polyacetylene due to its inherentinstability.

Another object of this invention is to provide a process for theproduction of the aforementioned polyacetylene composite.

A further object of this invention is to provide a method for the use ofthe polyacetylene composite.

These and other objects and characteristic features of the presentinvention will become apparent to those skilled in the art as thedisclosure is made in the following description of a preferredembodiment of the invention, as illustrated in the accompanyingdrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 through FIG. 6 are infrared absorption spectra.

FIG. 7 is a schematic cross section of a paper type battery.

FIG. 8 is a graph showing the results of a cycle test.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides a polyacetylene composite which comprises apolyacetylene polymer and a coating formed on the polyacetylene polymerwith at least one of the ionic organic compounds represented by thegeneral formula (I): ##STR4## (Wherein M denotes at least one memberselected from the group of alkali metals, X and Y are the same ordifferent and represent --O or ##STR5## R₁, R₂, R₃, and R₄ each are atleast one member selected from the group consisting of hydrogensubstituted or unsubstituted alkyl groups of 1 to 5 carbon atoms, andsubstituted or unsubstituted alkoxy groups of 1 to 5 carbon atoms, or R₁and R₂ or R₃ and R₄ in combination form a cyclic structure).

The term "ionic organic compounds" as used in the present inventionmeans alkoxide derivatives or semicarbonic ester derivatives of 1,2-diolrepresented by the general formula (I), wherein M is an alkali metalsuch as lithium, sodium, potassium and the like.

In the general formula (I), X and Y are the same or different andrepresent --O or ##STR6## R₁, R₂, R₃, and R₄ are at least one memberselected from the group consisting of hydrogen, substituted orunsubstituted alkyl groups of 1 to 5 carbon atoms, and substituted orunsubstituted alkoxy groups of 1 to 5 carbon atoms. If theaforementioned number of carbon atoms of substituted or unsubstitutedalkyl groups and substituted or unsubstituted alkoxy groups is 6 ormore, the effects by forming composites to be described are poor and,therefore, the carbon number of the aforementioned alkyl or alkoxygroups should be not more than 5. The cyclic structure may be formed bya combination of R₁ and R₂ or R₃ and R₄.

The first group of the ionic organic compounds includes alkali metalalkoxide type compounds of 1,2-diol, which compounds are obtained byreaction of 1,2-diol with alkali metals or with organic alkali metalcompounds.

Examples of these compounds are as follows. ##STR7##

The second group of the ionic organic compounds includes semicarbonicester derivatives of 1,2-diol which may be obtained by reaction of1,2-diol with phosgene.

Examples of such compounds are as follows. ##STR8##

The third group includes ortho-ester derivatives which are representedby, for example, the general formula (II): ##STR9## (wherein M denotesat least one member selected from the group of alkali metals, Z₁ and Z₂are the same or different and each denotes a straight-chain alkylenegroup of 2 to 5 carbon atoms, a group wherein hydrogen atoms of astraight-chain alkylene group of 2 to 5 carbon atoms are substituted byat least one substituent selected from the class consisting of halogenatoms, alkyl groups, and aryl groups, or a group of the formula of##STR10## where n denotes an integer of the value of 2 to 5).

The number of carbon atoms of the substituted or unsubstitutedstraight-chain alkylene group in the general formula (II) is in therange of 2 to 5. If the aforementioned number of carbon atoms is 6 ormore, the ability of the compound to interreact with the cation speciesis too low to conform to the spirit of this invention. If the number ofcarbon atoms is 1, the synthesis of the compound becomes difficult. Thevalue of the integer denoted by n in the group of the formula ##STR11##in the general formula (II) is selected in the range of 3 to 5. If thisvalue is 2 or less, the ring is deformed so heavily as to jeopardize itsstability. If the value is 6 or more, the synthesis of the compoundbecomes difficult.

The substituents available for the substituted straight-chain alkylenegroup include halogen atoms, alkyl groups, and aryl groups. As thehalogen atoms available for the substitution, there may be citedfluorine, chlorine, bromine, and iodine. As the alkyl groups and arylgroups available for the substitution, there may be cited methyl, ethyl,n-propyl, iso-butyl, n-pentyl, phenyl, tolyl, naphthyl, 4-methoxyphenyl,and 4-chlorophenyl groups.

There may be cited another method which produces the ortho-esterderivatives by subjecting cyclic carbonic esters represented by thegeneral formula (III): ##STR12## (wherein Z denotes a straight-chainalkylene group of 2 to 5 carbon atoms, a group wherein hydrogen atoms ofa straight-chain alkylene group of 2 to 5 carbon atoms are substitutedby at least one substituent selected from the class consisting ofhalogen atoms, alkyl groups, and aryl groups, or a group of the formulaof ##STR13## where n denotes an integer of the value of 3 to 5) to areductive coupling reaction. As methods for the reductive coupling,

(a) the method which causes the compounds represented by the generalformula (III) to react with organic metal complexes of alkali metalssuch as lithium, sodium, or potassium and biphenyl, naphthalene, oranthracene

(b) the method which causes the same compounds to be electrochemicallyreduced in a supporting electrolyte containing at least one alkali metalion such as lithium ion, sodium ion, or potassium ion

may be cited, for example.

The method of (a) is accomplished specifically by causing the compoundsof the general formula (III) to react with the organic metal complexesin a solvent such as tetrahydrofuran, dimethoxy ethane, diethoxy ethane,or diethyl ether, for example. Although the reaction temperature is notspecifically defined, it may be selected in the range of -100° C. to100° C.

The method of (b) is effected specifically by inducing electrochemicalreduction in an electrolytic solution comprising an electrolyte whichwill be described more fully afterward, the compounds of the generalformula (III), and optionally a solvent. The reducing potential in thiselectrochemical reduction is generally selected in the range of -0.1 Vto +2.5 V relative to the lithium standard electrode. In these methods,the ortho-ester derivatives are formed on or near the surface of theelectrode. The novel ortho-ester derivatives of the present inventionare stable in the absence of a protonic compound such as water andpossess an ability to conduct solid ions electrically and interact withalkali metal ions. Thus, they prove highly useful compounds.

Examples of the novel ortho-ester derivatives of the present inventionand the cyclic carbonic esters as respective starting substances areshown in the following table.

    __________________________________________________________________________    Cyclic carbonic ester                                                                     M  Ortho-ester derivative                                         __________________________________________________________________________     ##STR14##  Li                                                                                ##STR15##                                                      ##STR16##  Li                                                                                ##STR17##                                                      ##STR18##  Na                                                                                ##STR19##                                                      ##STR20##  K                                                                                 ##STR21##                                                      ##STR22##  Li                                                                                ##STR23##                                                     __________________________________________________________________________

Since the ionic organic compounds of the present invention possess anability to conduct ions electrically and interact with alkali metalions, they manifest marvelous effects when they are combined withn-doped polyacetylene. To be specific, they bring about a prominenteffect of stabilizing profoundly the n-doped polyacetylene when they areapplied as a coating on the n-doped polyacetylene.

The term "polyacetylene" as used in this invention means a product whichis easily obtained in the form of film, power, or gel by polymerizingacetylene in the presence of a Ziegler type catalyst formed of atransition metal compound and an organic metal compound or a catalystformed of a transition metal compound and a reducing agent, whennecessary, in conjunction with a copolymerizable monomer. It is awell-known fact that the polyacetylene readily undergoes the p-typedoping through the reaction with an electron accepting compound orthrough an electrochemical oxidation, and the n-type doping through thereaction with an electron donating compound or through anelectrochemical reduction. Particularly, the n-doped polyacetylenepossesses the specific nature as described above and, despite thisfeature, has found no utility in actual applications because of itsinstability.

When the ionic organic compound is applied as a coating on the n-dopedpolyacetylene, it confers upon the polyacetylene notably high stabilityto withstand the actions of oxygen, carbon dioxide gas, and reactivesolvents. This coating also manifests a truly striking effect withrespect to the electrochemical reversible stability as described morefully afterward. The coating amount is in the range of 10-300 parts byweight, preferably 50-200 parts by weight, and more preferably 75-100parts by weight, based on polyacetylene of 100 parts by weight. As amethod for forming this coating, the method which comprises dissolvingthe ionic organic compound in a solvent and applying the resultantsolution on the polyacetylene or the n-doped polyacetylene can be citedin the first place. The solvent to be used for this solution is desiredto be a aprotic solvent such as dimethyl formamide, dimethyl acetamide,or dimethyl sulfoxide.

As another method available for the formation of the coating, the methodwhich uses polyacetylene as an electrode and causes the ionic organiccompound to be directly deposited in the form of a coating on thesurface of that electrode through electrochemical reduction may becited. This method is suitable to form a very thin coating. This methodis carried out by preparing an elecrolytic solution containing a cycliccarbonic ester compound represented by the aforementioned generalformula (III) and at least one ion selected from the group consisting ofthe alkali metal ions such as Li⁺, Na⁺, and K⁺, placing polyacetylene asan electrode in the electrolytic solution, and inducing electrochemicalreduction in the system. By this procedure, the formation of theorthoester derivative and the n-doping of polyacetylene proceedsimultaneously.

In this case, the cyclic carbonic ester may be used directly as asolvent for the electrolytic solution or it may be used in the formdiluted with or dissolved in some other solvent. The amount of thecyclic carbonic ester to be used is desired to fall in the range of 0.1to 100% by weight (the weight exclusive of electrolyte), preferably 10to 100% by weight, based on the solvents of the electrolytic solution.As other solvent usable in the electrolytic solution, there is selectedan aprotic solvent which is electrochemically stable in the range ofpotential favoring the progress of the reduction. Examples of thesolvent are tetrahydrofuran, methyl tetrahydrofuran, dimethoxyethane,diethyl ether, acetonitrile, propionitrile, benzene, toluene, xylene,and anisole.

Examples of the electrolyte used for the formation of the electrolyticsolution include LiClO₄, LiCl, LiBF₄, LiBr, LiPF₆, CH₃ SO₃ Li, CF₃ SO₃Li, NaClO₄, NaBF₄, NaPF₆, CH₃ SO₃ Na, CF₃ SO₃ Na, KPF₆, CH₃ SO₃ K, andCF₃ SO₃ K.

The potential range for the promotion of the electrochemical reductionfalls in the range of -0.1 V to +2.5 V relative to the lithium standardelectrode potential, preferably in the range of 0.0 V to +1.8 V in thecase of lithium ion, in the range of +0.3 V to +1.8 V in the case ofsodium ion, or in the range of +0.1 V to +1.8 V in the case of potassiumion. The total quantity of electricity to be supplied for the sake ofthe electrochemical reduction is desired to be an equivalent in therange of 30 to 80 mol%, preferably 35 to 70 mol%, per the CH unit ofpolyacetylene.

Here, the quantity of electricity, Q (in ampere hour), equivalent to thedoping amount, A mol%, per the CH unit of polyacetylene is calculatedbased on the following formula. ##EQU1##

In the formula, W stands for the weight (in gram) of the polyacetyleneused.

As described above, the n-doped polyacetylene, when coated with theionic organic compound of this invention, is profoundly stabilized andvested with electrochemically highly stable reversibility and is enabledto manifest an outstanding performance as a negative electrode activesubstance in the non-aqueous type secondary battery or solid electrolytetype secondary battery. In the production of such a secondary battery,the n-doped or undoped polyacetylene coated with the ionic organiccompound of the present invention obtained by the aforementioned methodmay be incorporated as a negative electrode. In the case of anon-aqueous type secondary battery, the aforementioned solution preparedfor the electrochemical coating treatment can be advantageously used asthe electrolytic solution in the secondary battery because it effects anelectrochemical coating treatment of naked polyacetylene during theinitial charging. Although the positive electrode active substance forthe secondary battery is not specifically defined, it may be freelyselected from among such positive electrode active substances as FeS₂,TiS₂, TiS₃, MnO₂, Li_(1-x) CoO₂ (wherein 0≦×≦1), V₂ O₅, MoO₃, CuF₂,halogen such as iodine, bromine, chlorine, etc., P-type polyacetylene,P-type polyparaphenylene, and P-type polypyrrole.

As non-aqueous electrolytic solutions, the solutions which are obtainedby dissolving electrolytes represented by LiClO₄, LiCL, LiBr, LiBF₄,LiPF₆, NaClO₄, NaBF₄, NaPF₆, CH₃ SO₃ K, CF₃ SO₃ K, and KPF₆ in organicsolvents represented by tetrahydrofuran, dimethoxyethane, solfolan,methylsulfolan, propylene carbonate, ethylene carbonate,Υ-butyrolactone, acetonitrile, and propionitrile may be used.

Although the solid electrolyte for use in the electrolytic solution isnot specifically defined, it may be selected from among LiI, LiI(Al₂O₃), Li₃ N, Na₃ Zr₂ Si₂ PO₁₂, and K₂ O 5.2Fe₂ O₃ 0.8ZnO.

The n-doped polyacetylene coated with the ionic organic compound of thisinvention is highly stable and the secondary battery which uses thecoated n-doped polyacetylene mentioned above as a negative electrodeactive substance amazingly excels the conventional n-type polyacetylenein terms of protracted charge-discharge cycle property, self-dischargeproperty, and voltage-maintaining property and proves to be a highlyuseful secondary battery of novel principle.

Now, the present invention will be described more specifically belowwith reference to working examples.

TEST 1 (Preparation of polyacetylene)

This test represents a procedure for the preparation of polyacetylene tobe used in the following working examples.

In a glass vessel having an inner volume of 800 ml and under anatmosphere of N₂ gas, a catalyst was prepared by adding 6 ml oftetrabutoxy titanium and 10 ml of triethyl aluminum to 50 ml of toluene.The vessel was cooled to -78° C., evacuated of the inner gas, swirled toallow the catalyst to be deposited on the inner wall surface thereof,and then supplied with acetylene gas. Immediately a film ofpolyacetylene was formed on the inner wall surface of the vessel. Thevessel was left standing for 15 minutes and evacuated of the inner gas.The film was washed five times with 0.5N-HCl-methanol, then dried, andtaken out of the vessel.

This film of polyacetylene was thermally treated at 250° C. for fiveseconds, and then put to use in the following examples.

TEST 2

In 100 ml of tetrahydrofuran was dissolved 1.28 g of naphthalene and0.14 g of lithium metal was added thereto. The resultant solution wasstirred at room temperature for two hours to afford lithium-naphthalenecomplex. When 2.5 g of propylene carbonate was added dropwise to theresultant solution, a light brown precipitate occurred immediately. Thisprecipitate was separated by filtration under N₂, washed with benzene,and dried. Consequently, there was obtained 2.1 g of powdery product.

The results of analyses of this powdery product are shown in Table 1 andFIG. 2. The molecular weight of this product was determined by thecryoscopic method using dimethyl sulfoxide as the solvent.

The N.M.R. was determined in the DMSO-d6 solvent and the infraredspectrum measured by the KBr method.

                                      TABLE 1                                     __________________________________________________________________________                                 1H                                                       Molecular weight                                                                        Elementary analysis                                                                      (60 MHz)                                                                            Infrared                                   Melting Point                                                                         Found                                                                             Calculated                                                                          Found                                                                              Calculated                                                                          N.M.R. δ                                                                      spectrum                                   __________________________________________________________________________    150° C.                                                                        223 218   C:                                                                              0.437                                                                            C: 0.440                                                                            1.32(d,3H)                                                                          FIG. 1                                     minimum           H:                                                                              0.058                                                                            H: 0.055                                                                            4.05(t,1H)                                       (decom-           O:                                                                              0.443                                                                            O: 0.440                                                                            4.31(t,1H)                                       position)                                                                                       Li:                                                                             0.062                                                                            Li:                                                                              0.064                                                                            4.73(m,1H)                                       __________________________________________________________________________

TEST 3

In 100 ml of dimethoxyethane was dissolved 1.54 g of biphenyl and 0.46 gof sodium metal was added thereto. The resultant solution was stirred atroom temperature for two hours, to afford a sodium-biphenyl complex.When 2.5 g of ethylene carbonate was added to the resultant solution, alight brown precipitate occurred immediately. This precipitate wasseparated by filtration under N₂, washed with benzene, and then dried toobtain 1.9 g of powdery product.

This powdery product was analyzed similarly to the product of Test 2.The results are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                                  1H                                                      Molecular weight                                                                        Elementary analysis                                                                       (60 MHz)                                                                            Infrared                                  Melting point                                                                         Found                                                                             Calculated                                                                          Found Calculated                                                                          N.M.R.                                                                              spectrum                                  __________________________________________________________________________    150° C.                                                                        109 111   C: 0.327                                                                            C: 0.324                                                                            3.19(s)                                                                             2950 cm.sup.-1                            minimum           H: 0.039                                                                            H: 0.036    2850 cm.sup.-1                            (decomposition)   O: 0.429                                                                            O: 0.432    1640 cm.sup.-1                                              Na:                                                                              0.203                                                                            Na:                                                                              0.207    1400 cm.sup.-1                                                                1315 cm.sup.-1                                                                1095 cm.sup.-1                            __________________________________________________________________________

TESTS 4-6

In 100 ml of tetrahydrofuran was dissolved 1.78 g of anthracene and 0.46g of potassium metal was added thereto. The resultant solution wasstirred at room temperature for two hours, to afford apotassium-anthracene complex. When 2.5 g of a varying cyclic carbonicester indicated in Table 3 was added to the resultant solution, a lightbrown precipitate invariably occurred immediately. By treating theprecipitate by following the procedure of Test 2, there was invariablyobtained a powdered product.

The results of analyses of the various products thus obtained are shownin Table 3.

                  TABLE 3                                                         ______________________________________                                                 Test 4      Test 5      Test 6                                       Cyclic   1,3-Propanediol                                                                           1,4-Butanediol                                                                            1,5-Pentanediol                              carbonic ester                                                                         carbonic ester                                                                            carbonic ester                                                                            carbonic ester                               ______________________________________                                        Elementary                                                                    analyses                                                                      Found values                                                                           C: 0.335    C: 0.381    C: 0.431                                              H: 0.044    H: 0.059    H: 0.057                                              O: 0.341    O: 0.309    O: 0.286                                              K: 0.284    K: 0.253    K: 0.231                                     Calculated                                                                             C: 0.338    C: 0.385    C: 0.424                                     values   H: 0.042    H: 0.051    H: 0.059                                              O: 0.338    O: 0.308    O: 0.282                                              K: 0.282    K: 0.256    K: 0.235                                     ______________________________________                                    

TEST 7 (Preparation of LiCoO₂)

This test represents a procedure for the preparation of LiCoO₂ to beused in the following working examples.

A mixture of 73.9 g of lithium carbonate and 149.9 g of cobalt oxide waspulverized and calcined in an electric furnace at 900° C. for two hours.

After cooling, the obtained blackish gray LiCoO₂ was pulverized, thenused in the following working examples.

EXAMPLE 1

A three-electrode electrochemical reaction system was set up by using a0.6M-LiClO₄ -propylene carbonate solution as an electrolytic solutionand disposing 13 mg of polyacetylene as a working electrode, 50 mg oflithium metal as an counter electrode, and a reference electrode oflithium. A constant current of 5 mA was passed for 2.3 hours with theoperating electrode as a cathode. During this operation, the quantity ofelectricity, Q, was 0.0115 Ahr equivalent to a doping amount, A, of42.9%. During the operation, the potential of the working electrode ofpolyacetylene relative to the reference electrode changed from +2.7 V to+0.1 V.

Then a constant current of 5 mA was passed with the working electrodeused as an anode. In this case, it took 1.1 hours for the potential ofthe working electrode to reach +2.5 V. Then, the electrolytic solutionwas withdrawn and the polyacetylene was washed with propylene carbonateand benzene in the order mentioned, and dried.

After the drying, the polyacetylene was tested for infrared spectrum.The infrared spectrum is shown in FIG. 2. The untreated polyacetylene,as a control, was subjected to the same test. The differential spectrumis shown in FIG. 3. The test results clearly testify the formation of acoating. The spectrum agreed with the spectrum (FIG. 1) of the productobtained in Test 2.

From the data, it is noted that the product obtained here was apolyacetylene composite having polyacetylene polymer coated with theortho-ester derivative obtained in Test 2.

Subsequently, this polyacetylene was immersed and washed in methanol andthen dried. The infrared spectrum obtained of the cleaned polyacetyleneis shown in FIG. 4. This spectrum agreed with the spectrum (FIG. 5) ofthe original polyacetylene.

COMPARATIVE EXPERIMENT 1

The procedure of Example 1 was repeated except that tetrahydrofuran wasused in the place of propylene carbonate. The infrared spectrum obtainedof the polyacetylene after it was washed with tetrahydrofuran is shownin FIG. 6. This infrared spectrum agreed with the spectrum of theoriginal polyacetylene, indicating that no coating was formed during thetreatment.

EXAMPLE 2

The electrochemical treatment of Example 1 was repeated by following theprocedure of Example 1, except that 1,3-propanediol carbonicester/benzene (50:50 is weight ratio) mixture was used in the place ofpropylene carbonate.

In this case, the quantity of electricity passed, Q, was 0.0113 Ahr,equivalent to a doping amount, A, of 42.2%. During the treatment, thepotential of the working electrode of polyacetylene relative to thereference electrode changed from 2.7 V to +0.1 V.

Then a constant current of 5 mA was passed with the working electrodeused as an anode. In this case, it took 1.1 hours for the potential toreach +2.5 V. The coating consequently formed was washed and dried byfollowing the procedure of Example 1.

An infrared spectrum was obtained of this polyacetylene. In thespectrum, absorption peaks appeared at 2850-3000 cm⁻¹, 1625 cm⁻¹, 1400cm⁻¹, 1315 cm⁻¹, and 1095 cm⁻¹ in addition to the absorption proper topolyacetylene. This spectrum agreed with the spectrum of the compoundobtained in Test 4.

EXAMPLE 3

The electrochemical treatment of Example 1 was repeated by following theprocedure of Example 1, except that a propylene carbonate/ethylenecarbonate mixture (50:50 by weight ratio) was used in the place ofpropylene carbonate.

During this treatment, the quantity of electricity passed, Q, was 0.0110Ahr, equivalent to a doping amount, A, of 41.0%. In this case, thepotential of the working electrode of polyacetylene relative to thereference electrode changed from 2.7 V to 0.1 V.

Then, a constant current of 5 mA was passed with the working electrodeas an anode. It took 1.1 hours for the potential to reach +2.5 V. Thecoating thus obtained was washed and dried by following the procedure ofExample 1. The infrared spectrum obtained of the cleaned coating showednew absorption peaks at 2850-3000 cm⁻¹ , 1635-1670 cm⁻¹, 1400-1410 cm⁻¹,1310-1320 cm⁻¹, and 1095 cm⁻¹.

EXAMPLE 4

A paper type battery having a cross section of FIG. 7 was triallyprepared by using 1.2 g of polyacetylene as a negative electrode. 3.7 gof LiCoO₂ as a positive electrode, and a 0.6M-LiClO₄ -propylenecarbonate solution as electrolytic solution.

In FIG. 7, 1 denotes an external film of Al-laminated polyethylene and 2a positive electrode current collector of platinum-plated nickel foil50μin thickness and 5 cm×5 cm in area. The collector 2 was fused withthe external film 1. Then, 3 denotes a positive electrode activesubstance, 4 a separator formed of non-woven fabric of polypropylene, 5a negative electrode active substance, and 6 a negative electrodecurrent collector formed of a nickel foil 50μin thickness and 5 cm×5 cmin area.

This battery was subjected to initial charging at a constant current of10 mA for 120 hours. In this case, the quantity of electricity passed,Q, was 1.2 Ahr, equivalent to a doping amount of 48.5%.

The battery was subjected to a constant current (50 mA) charge-dischargetest under the conditions of 4.5 V of final voltage for recharging and2.5 V of final voltage for discharging.

At the time of charging treatment, the battery showed characteristics ofopen circuit voltage of 4.45 V and the average discharge voltage of 4.1V. Table 4 and Table 5 show fundamental characteristics of the batteryat the time of cycling. FIG. 8a shows the results of a cycle test.

                  TABLE 4                                                         ______________________________________                                        Charging   Discharging                                                        characteristics                                                                          characteristics                                                         Electrical       Electrical                                                                            Current                                                                              Energy density                           Time quantity  Time   quantity                                                                              efficiency                                                                           (Total amount)                           ______________________________________                                        10.7 0.535 Ahr 10.3   0.519 Ahr                                                                             97.0%  161 Whr/kg                               hrs            hrs                                                            ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        (Self-discharge rate)                                                         Temp.    2 hours 24 hours   240 hours                                                                            720 hours                                  ______________________________________                                        20° C.                                                                          0%      1.5%       7.8%   10.8%                                      40° C.                                                                          0%      1.1%       5.3%    9.9%                                      ______________________________________                                    

EXAMPLE 5

The procedure of Example 4 was repeated except that the 0.6M-LiClO₄-propylene carbonate solution was replaced by a 0.6M-LiClO₄ -ethylenecarbonate/benzene (50:50 by weight ratio) solution.

This battery was subjected to initial charging at a constant current of10 mA for 120 hours. In this case, the quantity of electricity passed,Q, was 1.3 Ahr. equivalent to a doping amount of 52.5%.

The battery was subjected to a constant current (50 mA) charge-dischargetest under the conditions of 4.5 V of final voltage for recharging and2.5 V of final voltage for discharging.

At the time of charging treatment, the battery showed characteristics ofopen circuit voltage of 4.45 V and the average discharge voltage of 4.1V. Table 6 and Table 7 show fundamental characteristics of the batteryat the time of cycling.

EXAMPLE 6

The procedure of Example 4 was repeated except that the 0.6M-LiClO₄-propylene carbonate solution was replaced by a 0.6M-LiClO₄-γ-butyrolactone/ethylene carbonate (50:50 by weight ratio) solution.

This battery was subjected to initial charging at a constant current of10 mA for 120 hours. In this case, the quantity of electricity passed,Q, was 1.1 Ahr, equivalent to a doping amount of 44.5%.

The battery was subjected to a constant current (50 mA) charge-dischargetest under the conditions of 4.5 V of final voltage for recharging and2.5 V of final voltage for discharging.

At the time of charging treatment, the battery showed characteristics ofopen circuit voltage of 4.45 V and the average discharge voltage of 4.1V. Table 6 and Table 7 show fundamental characteristics of the batteryat the time of cycling.

COMPARATIVE EXPERIMENT 2

The procedure of Example 4 was repeated except that LiCoO₂ was replacedby 3.7 g of natural graphite.

From the start, this battery was subjected to a constant current (50 mA)charge-discharge test without initial electrochemical treatment, underthe conditions of 4.5 V of final voltage for recharging and 2.5 V offinal voltage for discharging.

In this case, the quantity of electricity passed, Q, during initialcharging, was 0.095 Ahr, equivalent to a doping amount of 8.6%.

The results are shown in Table 6, Table 7 and FIG. 8b.

                                      TABLE 6                                     __________________________________________________________________________           Charging characteristics                                                                  Discharging characteristics                                            Electrical  Electrical                                                                            Current                                                                            Energy density                                  Time quantity                                                                             Time quantity                                                                              efficiency                                                                         (Total amount)                           __________________________________________________________________________    Example 5                                                                            9.9 hrs                                                                            0.495 Ahr                                                                            9.1 hrs                                                                            0.455 Ahr                                                                             91.9%                                                                              141 Whr/kg                               Example 6                                                                            10.1 hrs                                                                           0.505 Ahr                                                                            9.3 hrs                                                                            0.465 Ahr                                                                             92.1%                                                                              144 Whr/kg                               Comparative                                                                          1.9 hrs                                                                            0.095 Ahr                                                                            1.3 hrs                                                                            0.065 Ahr                                                                             68.4%                                                                               20 Whr/kg                               Experiment 2                                                                  __________________________________________________________________________

                  TABLE 7                                                         ______________________________________                                        (Self-discharge rate at 20° C.)                                                2 hours                                                                              24 hours  240 hours 720 hours                                  ______________________________________                                        Example 5 0%       3.0%      8.9%    15.1%                                    Example 6 0%       1.7%      8.1%    13.9%                                    Comparative                                                                             13.1%    29.0%     ˜100%                                                                           --                                       Experiment 2                                                                  ______________________________________                                    

EXAMPLE 7

A dimethylformamide solution of ##STR24## was applied to a polyacetylenecoating and dried at 50° C. in a vacuum. This procedure was repeatedfive times. As a result, there was prepared a polyacetylene compositehaving a coating of ##STR25## of 77 parts by weight relative to 100parts by weight of polyacetylene.

A paper type battery shown in FIG. 7 was prepared by using the abovepolyacetylene composite of 2.3 g as a negative electrode, LiCoO₂ of 3.7g as a positive electrode, and a 0.3M-LiClO₄ -methylsulforan solution asan electrolytic solution.

The battery was subjected to a constant current (50 mA) charge-dischargecycle test under the conditions of 4.5 V of final voltage for rechargingand 2.5 V of final voltage for discharging. Changes of capacityretention arising along with the cycle test are shown in Table 8.

EXAMPLE 8

A dimethylformamide solution of ##STR26## was applied to a polyacetylenecoating and dried at 50° C. in a vacuum. This procedure was repeatedseven times. As a result, there was prepared a polyacetylene compositehaving a coating of ##STR27## of 91 parts by weight relative to 100parts by weight of polyacetylene.

A paper type battery shown in FIG. 7 was prepared by using the abovepolyacetylene composite of 2.5 g as a negative electrode, LiCoO₂ of 3.7g as a positive electrode, and a 0.3M-LiClO₄ -methylsulforan solution asan electrolytic solution.

The battery was subjected to a constant current (50 mA) charge-dischargecycle test under the conditions of 4.5 V of final voltage for rechargingand 2.5 V of final voltage for discharging. Changes of capacityretention arising along with the cycle test are shown in Table 8.

COMPARATIVE EXPERIMENT 3

The procedure of Example 7 was repeated, except that the ##STR28## wasnot used, to trially prepare a paper type battery shown in FIG. 7. Thebattery was subjected to the charge-discharge cycle test under the samecondition with Example 7. The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        (Capacity retention)                                                          Number of                                                                     cycle      10       25     50     100  200                                    ______________________________________                                        Example 7  98%      95%    90%    81%  73%                                    Example 8  99%      97%    93%    89%  89%                                    Comparative                                                                              81%      47%    29%    11%   9%                                    Experiment 3                                                                  ______________________________________                                    

What is claimed is:
 1. A process for the production of a polyacetylenecomposite, comprising applying to a polyacetylene polymer a solutioncontaining at least one ionic organic compound represented by thegeneral formula (I): ##STR29## the same or different and represent -O or##STR30## R₁, R₂, R₃, and R₄ each are at least one member selected fromthe group consisting of hydrogen substituted or unsubstituted alkylgroups of 1 to 5 carbon atoms, and substituted or unsubstituted alkoxygroups of 1 to 5 carbon atoms, or R₁ and R₂ or R₃ and R₄ in combinationform a cyclic structure, and drying the coated polyacetylene polymer.